For over a quarter of a century, a hydrogen-terminated Si(111) single crystalline surface has remained the gold standard as a starting point for silicon modification chemistry. Although such a surface, following its preparation, is susceptible to oxidation under ambient conditions, it has proven to be sufficiently stable for chemical transformations leading to a remarkably versatile set of linkages, including Si-Halogen, Si—C (in alkyls), and Si—O (in alkoxides). However, creating a well-defined and stable interface based on Si—N bonds has remained elusive. Despite the fact that treatment with azides, nitro compounds, and amines has been found to lead to the formation of surface Si—N, each of these modification schemes produces additional carbon- or oxygen-containing functional groups that in turn react with the surface itself, leaving contaminants that affect the interface properties for any further modification protocols. More importantly, these currently available approaches to the generation of Si—N surface species lead to a variety of products, making the design of uniform attachment schemes or contaminant-free interfaces with these surfaces as a starting point essentially impossible.